CN101911351A - Electrode for fuel cell having two kinds of hydrophilicity and method for preparing the same and membrane electrode assembly and fuel cell comprising the same - Google Patents

Electrode for fuel cell having two kinds of hydrophilicity and method for preparing the same and membrane electrode assembly and fuel cell comprising the same Download PDF

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Publication number
CN101911351A
CN101911351A CN2008801231595A CN200880123159A CN101911351A CN 101911351 A CN101911351 A CN 101911351A CN 2008801231595 A CN2008801231595 A CN 2008801231595A CN 200880123159 A CN200880123159 A CN 200880123159A CN 101911351 A CN101911351 A CN 101911351A
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fuel cell
electrode
catalyst layer
catalyst
ink
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金赫
郑盛旭
李昶松
李源镐
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LG Corp
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LG Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8636—Inert electrodes with catalytic activity, e.g. for fuel cells with a gradient in another property than porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • H01M8/0263—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant having meandering or serpentine paths
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2457—Grouping of fuel cells, e.g. stacking of fuel cells with both reactants being gaseous or vaporised
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

An electrode for a fuel cell includes a gas diffusion layer contacting with a separator having a channel and a catalyst layer interposed between the gas diffusion layer and an electrolyte membrane. The catalyst layer of the electrode has two portions with different hydrophilicities. A portion of the catalyst layer that faces a channel has a higher hydrophilicity than a portion that does not face a channel. This electrode may control hydrophilicity of the catalyst layer differently according to locations, so it is possible to keep an amount of moisture in an electrode in a suitable way, thereby improving the performance of the cell.

Description

Have two kinds of hydrophilic electrodes that are used for fuel cell and preparation method thereof and the membrane electrode assembly and the fuel cell that comprise this electrode
Technical field
The present invention relates to a kind of two kinds of hydrophilic electrodes that are used for fuel cell that have, the method for preparing this electrode, and the membrane electrode assembly and the fuel cell that comprise this electrode, more particularly, the present invention relates to a kind of electrode that is used for fuel cell of moisture of the layer of control catalyst effectively, prepare the method for this electrode, and the membrane electrode assembly and the fuel cell that comprise this electrode.
Background technology
Recently, because the exhaustion of predictable conventional energy resource as oil and coal, the interest of alternative energy source is grown with each passing day.Fuel cell is one of energy as an alternative, and its advantage is to have high efficiency, does not discharge as NO xAnd SO xThe pollutant and the quantity of fuel of use abundant, so fuel cell has attracted the public's attentiveness.
Fuel cell is the generating system that a kind of chemical energy with fuel and oxidant is converted into electric energy, generally uses hydrogen and hydrocarbon (as methyl alcohol or butane) to act as a fuel, and uses oxygen as oxidant.
In fuel cell, membrane electrode assembly (MEA) is the elementary cell that is used to generate electricity, and it comprises the anode and the negative electrode of dielectric film and the relative both sides that are formed on dielectric film.Fig. 1 illustrates the principle of fuel cell power generation, the reaction equation of fuel cell when chemical equation 1 expression uses hydrogen to act as a fuel.With reference to figure 1 and chemical equation 1, the fuel oxidation reaction occurs in anode with generation hydrogen ion and electronics, and hydrogen ion moves to negative electrode by dielectric film.Electronics and the hydrogen ion that passes dielectric film are at negative electrode and oxygen (oxidant) water generation reaction, and this reaction makes electronics move to external circuit.
Chemical equation 1
Anode: H 2→ 2H ++ 2e -
Negative electrode: 1/2O 2+ 2H ++ 2e -→ H 2O
Reaction equation: H 2+ 1/2O 2→ H 2O
Fig. 2 illustrates the common structure of the membrane electrode assembly that is used for fuel cell.With reference to figure 2, the membrane electrode assembly that is used for fuel cell comprises dielectric film 201, the anode electrode and the cathode electrode of the both sides relative with being positioned at dielectric film 201.Anode electrode and cathode electrode comprise catalyst layer 203,205 and gas diffusion layers 208 respectively.Gas diffusion layers comprises electrode base board 209a, 209b and is formed on microporous layers 207a, 207b on the electrode base board.
In fuel cell, the amount of moisture is the factor of decision battery performance.Should suitably keep being incorporated into the moisture of battery or the moisture that produces at electrode.
Specifically, also be that the moisture of product helps the ion migration in electrode.Yet, also be not enough to guarantee the ionic conductivity of fuel cell as the amount of the moisture that product produced, therefore fuel cell operation under wet condition usually.
Yet excessive moisture can block the micropore on catalyst layer or the gas diffusion layers.Therefore, the preferred fuel battery moves under low humidity state so that have only the moisture of aequum to be present in catalyst layer.
Simultaneously, when fuel cell operation under low excessively damp condition, owing to lack moisture, and the conductivity meeting variation of ion, the result has reduced the efficient of fuel cell.Therefore, just become key issue at suitable low moisture levels fuel cell operation.
In the past, the catalyst layer of the membrane electrode assembly of fuel cell is a kind ofly to contain catalyst and obtain from the ink coated substrate of aggressiveness by using, so catalyst layer is uniform fully.Therefore the moisture of control catalyst layer is difficult.
In this respect, the early stage publication of Japan discloses 2006-286330 number and has disclosed a kind of method that catalyst layer has the electrode of different hydrophilic for preparing, and it is to realize by with the compound with different hydrophilic catalyst particle being carried out surface-reformation.
Yet, press for and develop a kind of even under the low humidity service conditions, can suitably make the catalyst layer of the electrode of fuel cell keep the otherwise effective technique more of moisture.
Summary of the invention
Technical problem
Therefore, the purpose of this invention is to provide a kind of electrode that is used for fuel cell, it can keep moisture in the electrode to proper level by each regional hydrophily of control catalyst layer.
Technical scheme
To achieve these goals, the invention provides a kind of electrode that is used for fuel cell, it comprise and have the contacted gas diffusion layers of dividing plate of groove and be arranged on gas diffusion layers and dielectric film between catalyst layer, wherein, the catalyst layer of described electrode has the two parts with different hydrophilic, and catalyst layer has higher hydrophily facing to the part of groove with not comparing facing to the part of groove.
The inventor finds that the early stage publication of Japan discloses 2006-286330 number and disclosed a kind of catalyst layer that zone with different hydrophilic performance is arranged, but its effect is inadequate, because ignored the correlation between the moisture control of the position of groove and catalyst layer.For this reason, as shown in Figure 5, at the electrode that is used for fuel cell of the present invention, in the part 21 of dividing plate 210 facing to groove, promptly the hydrophily corresponding to the part of the catalyst layer 203,205 of the gas diffusion layers 208 that directly contacts with the gas with low humidity has improved, reduced the amount of the moisture of being taken away by gas thus, though and to a certain extent moisture be pulled away and can also have kept sufficient humidity.Therefore, because suitably kept the moisture in the battery, can improve the performance of battery.In electrode of the present invention, when the difference to the contact angle of water is 2 °-20 °,, but the invention is not restricted to this facing to the part of groove and not deemed appropriate facing to the hydrophilic difference between the part of groove.
The electrode that is used for fuel cell according to the present invention can be more useful for the fuel cell that moves under the low humidity condition, for example described electrode can be 0-70% in humidity, preferred 20-70% more preferably suitably keeps the required moisture of fuel cell operation under the low humidity condition of 30-60%.
In electrode of the present invention, except already present catalyst layer, catalyst layer preferably further comprises the hydrophily reinforcing agent to improve hydrophily facing to the part of groove.For example, catalyst layer can comprise metallic catalyst or the metallic catalyst on carbon-based supports facing to the part of groove; Polymeric ionomers; Be selected from TiO 2, SiO 2, zeolite, zirconia, cerium oxide, acid treatment ceramic particle or carbon, hydrophilic polymers and Al 2O 3In a kind of hydrophily reinforcing agent, or their mixture.The content that can set the hydrophily reinforcing agent makes that the weight ratio of metallic catalyst and hydrophily reinforcing agent is 1: 0.05-1, but be not limited thereto.
In electrode of the present invention, catalyst layer not can be the general catalyst layer that generally uses in the prior art facing to the part of groove, and it can comprise metallic catalyst or metallic catalyst on carbon-based supports and polymeric ionomers.
Another scheme of the present invention provides the method that a kind of preparation is used for the electrode of fuel cell, it comprises: (S1): preparation (a) comprises metallic catalyst or at the ink of formation first catalyst layer of the metallic catalyst on the carbon-based supports, polymeric ionomers and solvent with (b) comprise the ink of formation second catalyst layer of metallic catalyst or the metallic catalyst on carbon-based supports, polymeric ionomers, hydrophily reinforcing agent and solvent respectively; (S2): the ink that the mode by ink jet type spraying will form first and second catalyst layers sprays on dielectric film or the gas diffusion layers, be sprayed onto the ink that does not form second catalyst layer and be sprayed onto part so that form the ink of first catalyst layer, form catalyst layer thus facing to groove facing to the part of groove.
In this respect, the early stage publication of Japan disclose to have disclosed for 2006-286330 number a kind ofly comes the method for the hydrophilicity of control catalyst floor by surface-reforming catalyst particle, but the inventor finds that this routine techniques is for surface-other technology of reforming catalyst particle needs.Yet, in the method for the invention, when preparation forms the ink of catalyst layer, added and mixed the hydrophilic hydrophily reinforcing agent that can improve catalyst layer, therefore, this method is very simple and without any need for extra technology.
Above-mentioned electrode of the present invention can be used for membrane electrode assembly or fuel cell.
Description of drawings
Fig. 1 is the schematic diagram of diagram fuel cell power generation principle;
Fig. 2 is the schematic diagram of the common structure of diagram fuel cell membrane electrode assembly;
Ink that Fig. 3 forms first catalyst layer for diagram sprays respectively according to the present invention and the schematic diagram that forms the ink of second catalyst layer;
Fig. 4 is for schematically illustrating the plane graph of catalyst layer formed according to the present invention;
Fig. 5 is that schematically diagram formation is according to the cross-sectional view of electrode of the present invention;
Fig. 6 is the schematic diagram of diagram according to the fuel cell of one embodiment of the present invention.
Embodiment
Hereinafter will describe the electrode that is used for fuel cell of the present invention in detail according to its preparation method.Before beginning description, should be understood that, the term that uses in specification and the appended claims should not be construed as and only limits to general and literal meaning, but should allow the inventor term to be done make an explanation based on pairing meaning of technical scheme of the present invention and notion on the basis of suitable definition with best explanation.
At first, preparation (a) comprises metallic catalyst or at the ink of formation first catalyst layer of the metallic catalyst on the carbon-based supports, polymeric ionomers and solvent with (b) comprise the ink (S1) of formation second catalyst layer of metallic catalyst or the metallic catalyst on carbon-based supports, polymeric ionomers, hydrophily reinforcing agent and solvent respectively.
According to the ink of formation first catalyst layer of the present invention can use any formation catalyst layer used in the prior art ink and without limits.For example, the ink of formation catalyst layer can comprise metallic catalyst or the metallic catalyst on carbon-based supports; Polymeric ionomers and solvent.
Metallic catalyst can typically be and be selected from platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palldium alloy, platinum-molybdenum alloy, platinum-rhodium alloy and the platinum-transition metal alloy any, perhaps their mixture, however the invention is not restricted to this.
Carbon-based supports can be the material based on carbon, be preferably and be selected among graphite, carbon black, acetylene black, superconduct acetylene black (denta black), Ketjen black (ketjen black), activated carbon, mesoporous carbon, carbon nano-tube, carbon nano-fiber, carbon nanometer cone angle, carbon nano ring, carbon nanocoils, fullerene (C60) and the Super-P any or their mixture.
Polymeric ionomers can typically be Nafion from aggressiveness (nafion ionomer) or sulfonated polymer such as sulfonation polytrifluorostyrene.
The kind of fuel cell and the content that purposes can suitably be controlled polymeric ionomers in the ink that forms first catalyst layer, and based on 100 weight portion catalyst, its content is preferably the 15-45 weight portion, and this will explain in the back.In this scope, do not have covering catalyst layer excessively to carry out easily from aggressiveness, and on catalyst layer, formed satisfied ion migrating channels yet to guarantee the good migration of ion to guarantee the reaction between catalyst and the fuel.
Solvent can be any that is selected from water, butanols, isopropyl alcohol, methyl alcohol, ethanol, normal propyl alcohol, n-butyl acetate and the ethylene glycol, or their mixture.
In the ink that forms first catalyst layer, the kind of fuel cell or its preparation or environment for use can suitably be controlled the content of solvent.For example, based on 100 weight portion catalyst, the content of solvent can be the 100-5000 weight portion, but is not limited thereto.When the content of solvent was positioned at above-mentioned scope, energy optimum ground kept the viscosity of the ink of formation catalyst layer, and the fabulous dispersiveness that guarantees catalyst particle in application job thus is to form the catalyst layer of homogeneous.In addition, can finish application job, thereby guarantee fabulous productivity ratio with the shortest operating time.
Except adding the hydrophily reinforcing agent, can according to the identical method preparation of the ink that forms first catalyst layer ink according to formation second catalyst layer of the present invention.For example, the ink that forms second catalyst layer comprises metallic catalyst or the metallic catalyst on carbon-based supports; Polymeric ionomers; Hydrophily reinforcing agent and solvent.Described hydrophily reinforcing agent can be and is selected from TiO 2, SiO 2, zeolite, zirconia, cerium oxide, acid treatment ceramic particle or carbon, hydrophilic polymers and Al 2O 3In any, or their mixture, but be not limited thereto.
But the kind and the purposes that join the content fuel cell of the hydrophily reinforcing agent in the ink that forms second catalyst layer need be controlled through sufficient experimental evidence.For example, the weight ratio of metallic catalyst and hydrophily reinforcing agent can be set at 1: 0.05-1.In this scope, the catalyst layer of electrode can show fabulous ionic conductivity and not hinder material Transfer.Specifically, according to employed material, the hydrophily reinforcing agent can produce different hydrophilies.If described weight ratio is lower than above-mentioned scope, then hydrophilic effect can be insufficient.Yet, if described weight ratio is higher than above-mentioned scope, compares excessive hydrophily reinforcing agent with catalyst and can absorb too many moisture, this can produce the migration of bad influence and obstruction electronics to material Transfer, thereby has reduced the efficient of electrode.
As mentioned above after having prepared described ink, the ink that the mode by the ink jet type spraying will form first and second catalyst layers sprays on dielectric film or the gas diffusion layers.At this moment, the ink that forms first catalyst layer is sprayed onto not the part facing to groove, and the ink that forms second catalyst layer is sprayed onto the part facing to groove, forms catalyst layer (S2) thus.
As shown in Figure 3, forming the ink 11 of first catalyst layer and the ink 12 of formation second catalyst layer is sprayed onto on dielectric film 201 or the gas diffusion layers 208.The ink jet type spraying can use relevant software very accurately to adjust the spraying position of ink droplet, and the single ink droplet that therefore forms the ink 11 of first catalyst layer and the ink 12 that forms second catalyst layer can be sprayed onto on the default position of dielectric film 201 or gas diffusion layers 208.Therefore, as shown in Figure 4, the ink that forms second catalyst layer can be sprayed to the ink that will form first catalyst layer facing to the part 21 of groove and spray to not part 22 facing to groove.
By this method, though fuel cell has the pattern of multiple groove, but the ink of formation first and second catalyst layers of the present invention can be sprayed to facing to the part of groove with not facing to the part of groove any zone that therefore can the control catalyst layer respectively according to the position adjustment with different hydrophilic.
As shown in Figure 5, catalyst layer in the face of the part 21 of groove and dielectric film and gas diffusion layers in the face of the part of groove, have the gas flow of relatively low humidity, thereby moisture content taken away.Therefore, the catalyst layer 203,205 of corresponding these parts is compared with other parts and is had lower moisture concentration.Therefore, catalyst layer 203,205 of the present invention is set so that, too many moisture is taken away by gas in the face of the part 21 of groove has higher hydrophily with not comparing in the face of the part 22 of groove.In addition, though moisture taken away by gas because higher hydrophily can keep the skin wet at an easy rate, so the moisture of whole catalyst layer can keep balance.
Can measure facing to the part of groove with not facing to the hydrophilic difference between the part of groove with several different methods.For example, this species diversity can be represented with the contact angle to water.In the present invention, preferred more than 5 ° when the difference to the contact angle of water is more than 2 °, in the time of more preferably more than 10 °,, but the invention is not restricted to this facing to the part of groove and not deemed appropriate facing to the hydrophilic difference between the part of groove.If hydrophilic difference is too big, then can reduce the reactivity of catalyst layer.Therefore, when the difference to the contact angle of water was 2 °-20 °, the hydrophilic difference of catalyst layer was deemed appropriate.
When the ink droplet that forms first and second catalyst layers is sprayed onto on the precalculated position of dielectric film adjacent one another are or gas diffusion layers, formed catalyst layer according to said method.When the ink droplet that forms first and second catalyst layers is repeatedly sprayed on the catalyst layer of formation, can obtain the catalyst layer of desired thickness according to said method.
After finishing the ink spray procedure, can further carry out drying program and come dried catalyst layer.In this case, the dry run for the ink droplet accelerating to spray can spray ink with condition of heat treatment in the ink spraying process.
Can suitably select heat-treat condition according to production environment and productivity ratio.For example, heat treatment can preferably be carried out under 25-30 ℃ under 20-90 ℃, but is not restrictive.
As mentioned above, in the present invention, because the position catalyst layer according to groove has different hydrophilies, those of ordinary skill in the art just can expect the amount of coming the moisture in the control electrode suitably by the concentration of adjusting catalyst layer moisture fully without any need for experience.
The electrode that is used for fuel cell according to the present invention has higher hydrophily in the part of needs, so it can be more useful for the fuel cell that moves under the low humidity condition.For example, described electrode is 0-70% in humidity, and preferred 20-70% more preferably can suitably keep the required moisture of fuel cell operation under the low humidity condition of 30-60%, and therefore keeps fuel cell performance under splendid state.
The electrode that is used for fuel cell according to the present invention can be formed on dielectric film or gas diffusion layers, so it can be used to prepare the membrane electrode assembly that is used for fuel cell according to the present invention.
As shown in Figure 2, the membrane electrode assembly that is used for fuel cell according to the present invention comprises: dielectric film 201; Anode and negative electrode with the relative both sides that are positioned at dielectric film 201.Described anode and negative electrode can comprise gas diffusion layers 208 and catalyst layer 203 and 205 respectively.The gas diffusion layers 208 that is used for fuel cell according to the present invention can comprise substrate 209a and 209b respectively and be formed on substrate 209a and the microporous layers 207a and the 207b of 209b one side.
Be used for any dielectric film that dielectric film of the present invention can adopt prior art to use, for example be selected from any polymer in polybenzimidazoles, polyether-ketone, polysulfones or their bronsted lowry acids and bases bronsted lowry of perfluorinated sulfonic acid polymer, polymer, polyimides, polyvinylidene fluoride, polyether sulfone, polyphenylene sulfide, polyphenylene oxide, polyphosphazene (polyphosphazene), Polyethylene Naphthalate, polyester, doping, but the invention is not restricted to this based on hydrocarbon.
Being used for gas diffusion layers of the present invention plays the effect of conductor and becomes as the gas of reactant with as the passage of the water of product between dividing plate and catalyst layer.Therefore, gas diffusion layers has loose structure (porosity with 20-90%) and makes gas easily to pass through.
Gas diffusion layers can adopt any gas diffusion layers that uses in the prior art, and it generally can comprise by any electrically-conductive backing plate made that is selected from carbon paper, carbon cloth and the carbon felt.Gas diffusion layers can further comprise the microporous layers that is formed on electrically-conductive backing plate one side, and microporous layers can be by making based on the material of carbon or based on the resin of fluorine.
Described material based on carbon can be and is selected among graphite, carbon black, acetylene black, superconduct acetylene black, Ketjen black, activated carbon, mesoporous carbon, carbon nano-tube, carbon nano-fiber, carbon nanohorn, carbon nano ring, carbon nanocoils, fullerene (C60) and the Super-P any, or their mixture, but the present invention is not limited to this.
Described resin based on fluorine can be and is selected from polytetrafluoroethylene, polyvinylidene fluoride (PVdF), polyvinyl alcohol, cellulose acetate, polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP) and the butadiene-styrene rubber (SBR) any, or their mixture, but the present invention is not limited to this.
Gas diffusion layers can have suitable thickness as required, 100-400 μ m for example, but be not limited thereto.If the thickness of gas diffusion layers is too little, then the resistance that electrically contacts between catalyst layer and the dividing plate increases, and gas diffusion layers may not have enough card compressions of trying hard to keep.If thickness is too big, then gas reactant can not move at an easy rate.Therefore, the thickness of gas diffusion layers should remain on proper level.
Simultaneously, catalyst layer is formed on the microporous layers of gas diffusion layers.
The present invention also provides a kind of fuel cell that comprises above-mentioned membrane electrode assembly.Fig. 6 is the schematic diagram of diagram according to the fuel cell of one embodiment of the present invention.With reference to figure 6, fuel cell of the present invention comprises that pile 200, fuel provide unit 400 and oxidant that unit 300 is provided.
Described pile 200 comprises at least a membrane electrode assembly of the present invention, and when comprising at least two kinds of membrane electrode assemblies, pile 200 comprises the dividing plate that is arranged between the membrane electrode assembly.Described dividing plate block film electrode assemblie is electrically connected each other, and fuel and oxidant that the outside provides are transferred to membrane electrode assembly.
Described fuel provides unit 400 to provide fuel to pile 200, and can comprise that tanks 410 that is used for storage of fuels and the fuel that is used for being stored in tanks 410 offer the pump 420 of pile 200.Fuel can be gaseous state or liquid hydrogen or hydrocarbon fuel, and hydrocarbon fuel for example can be methyl alcohol, ethanol, propyl alcohol, butanols or natural gas.
Described oxidant provides unit 300 to provide oxidant to pile 200.Oxidant is generally oxygen, and oxidant provides unit 300 to can be the pump of pumping oxygen or air.
Industrial applicibility
The electrode that is used for fuel cell according to the present invention can be according to the different hydrophilies that control catalyst layer in position, therefore can keep by rights the amount of moisture in the electrode and prevent near the shortage of the moisture of groove, improve thus the performance of battery.
Specifically, the electrode that is used for fuel cell according to the present invention is more suitable for the fuel cell that moves under the low humidity condition.

Claims (12)

1. electrode that is used for fuel cell, it comprises: and have the contacted gas diffusion layers of dividing plate of groove and be arranged on catalyst layer between described gas diffusion layers and the dielectric film, wherein, the catalyst layer of described electrode has the two parts with different hydrophilic, and catalyst layer has higher hydrophily facing to the part of groove with not comparing facing to the part of groove.
2. the electrode that is used for fuel cell according to claim 1, wherein, described part with different hydrophilic is 2 °-20 ° to the difference of the contact angle of water.
3. the electrode that is used for fuel cell according to claim 1, wherein, the fuel cell that uses described electrode is to move under the low humidity condition of humidity as 0-70%.
4. the electrode that is used for fuel cell according to claim 1, wherein, described catalyst layer comprises metallic catalyst or the metallic catalyst on carbon-based supports facing to the part of groove; Polymeric ionomers; Be selected from TiO 2, SiO 2, zeolite, zirconia, cerium oxide, acid treatment ceramic particle or carbon, hydrophilic polymers and Al 2O 3In a kind of hydrophily reinforcing agent, or their mixture.
5. the electrode that is used for fuel cell according to claim 1, wherein, described catalyst layer does not comprise metallic catalyst or metallic catalyst on carbon-based supports and polymeric ionomers facing to the part of groove.
6. the electrode that is used for fuel cell according to claim 4, wherein, the weight ratio of described metallic catalyst and described hydrophily reinforcing agent is 1: 0.05-1.
7. method for preparing the electrode that is used for fuel cell, it comprises:
(S1): preparation (a) comprises metallic catalyst or at the ink of formation first catalyst layer of the metallic catalyst on the carbon-based supports, polymeric ionomers and solvent with (b) comprise the ink of formation second catalyst layer of metallic catalyst or the metallic catalyst on carbon-based supports, polymeric ionomers, hydrophily reinforcing agent and solvent respectively; With
(S2): the ink that the mode by ink jet type spraying will form first and second catalyst layers sprays on dielectric film or the gas diffusion layers, be sprayed onto the ink that does not form second catalyst layer and be sprayed onto part so that form the ink of first catalyst layer, form catalyst layer thus facing to groove facing to the part of groove.
8. preparation according to claim 7 is used for the method for the electrode of fuel cell, wherein, after having prepared the described electrode that is used for fuel cell, described facing to the part of groove be not 2 °-20 ° facing to the difference to the contact angle of water between the part of groove.
9. preparation according to claim 7 is used for the method for the electrode of fuel cell, and wherein, the fuel cell that uses described electrode is to move under the low humidity condition of humidity as 0-70%.
10. preparation according to claim 7 is used for the method for the electrode of fuel cell, and wherein, in the ink that forms second catalyst layer, the hydrophily reinforcing agent is selected from TiO 2, SiO 2, zeolite, zirconia, cerium oxide, acid treatment ceramic particle or carbon, hydrophilic polymers and Al 2O 3In, perhaps be their mixture.
11. a membrane electrode assembly that is used for fuel cell, it comprises: dielectric film, and with the anode and the negative electrode of the relative both sides that are respectively formed at dielectric film, anode and negative electrode have catalyst layer and gas diffusion layers separately,
Wherein, described anode and negative electrode are the electrode that is used for fuel cell of each definition among the claim 1-6.
12. a fuel cell, it comprises:
Pile, it has
The membrane electrode assembly of one or more claims 11 definition and be arranged on dividing plate between the described membrane electrode assembly;
Be used for providing the fuel of fuel that the unit is provided to described pile; With
Be used for providing the oxidant of oxidant that the unit is provided to described pile.
CN2008801231595A 2007-12-28 2008-12-23 Electrode for fuel cell having two kinds of hydrophilicity and method for preparing the same and membrane electrode assembly and fuel cell comprising the same Pending CN101911351A (en)

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PCT/KR2008/007615 WO2009084846A2 (en) 2007-12-28 2008-12-23 Electrode for fuel cell having two kinds of hydrophilicity and method for preparing the same and membrane electrode assembly and fuel cell comprising the same

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